High-index glass elements



2,726,161 Patented Dec. 6, 1 955 United States PatentOfifice HIGH-INDEX GLASS ELEMENTS No Drawing. Application September 21, 1953, 2

Serial No. 381,502

6 Claims. (Cl. 106-47) This application is a continuation-in-part of our copending application Ser. No. 251,128, filed October 12, 1951 as a continuation-in-part of Ser. No. 56,055, filed Oct.-22, .1948 (now abandoned).

This invention relates to transparent high-index glass elements, such as glassbeads, fibers, flakes and thin plates, as new and useful articles of manufacture. These glass elements have a thickness not exceeding approximately two millimeters and have extraordinarily high refractive indices (2.1 to 2.5). They have high optical dispersion values and high dielectric constants. They are chemically stable and stable to sunlight and to exposure to humid atmospheres, and are not damaged by immersion in water. They can be made so as to-be substantially colorless, or they can be colored, if desired, by inclusion of suitable color-imparting metal compounds or other agents.

sutficiently to form transparent spheres by the action We utilizenovel glass compositions containing a subof surface tension while moving through air followed by rapid coolingto harden the spheres without devitrification taking place. The cullet can be made by quenching a streamof molten glass in water. The beads can also be made directly from a batch of molten glass;

The small size of the beads can be appreciated from the fact that there are billions in a mass thereof occupyinga cubic foot of volume, andthat a layer of bead contains many thousands per square inch..

Fibers can be made by jet-blowing a stream of molten glassp Filaments can be drawn from molten glass through a die, followed by rapid cooling. Thin plates and flakes of glass can be made by casting a thin layer ofmolten glass on a cold steel surface. Many of our glasses have been tested in the form of thin plates and have been found to have dielectric constants up to about 60, indicating suitability for use as dielectric elements of capacitors, etc. Small jewelry gems can be made from pieces of our glass. The high refractive, index and high optical dispersion results in high surface sparkle and high internal light reflection.

Our glasses lie outside the field of optical glasses as ordinarily conceived. Our glass beads are not made from true optical glasses but from novel compositions which wouldnot be regarded as optical glasses by glass technologists since they cannot be used for the purposes which a glass technologist has inmind'when he uses the term optical glass (namely, glasses useful for making high quality lenses and prisms for optical' instruments-such as cameras, projectors, microscopes, telescopes, periscopes, binoculars, spectacles, etc.). The manufacture of glass elements for suchoptical instruments generallyrequires the making of glass blanks of substantial sizeandthickness. The necessary pieces of solid glass must beformed from molten glass without Q devitrification taking place during the cooling of the manufacture of reflex-reflecting products of the type described in U. S. Patent No. 2,407,680 (Sept. 17, 1946); Glass beads for this usage have a diameter 'which may range from less than 1 mil up to about 10 mils. The

reflector products are used in-making highway and ve compositions which melt to a free-flowing state, since 1 the molten particles of glass must form themselves into true spheres due to the surface tension effect operating during the available time interval in the manufacturing process. The beads should be hogorneneous and transparent, and have a nearly perfect spherieity, in order to function properly as sphere-lenses. We have achieved these objectives withour novel glass compositions which provide beads having refractive indices ,in the desired range of 2.1 and higher. 1

The beads can be made byfusing'particles of glass cullet which are blown or dropped through a high temglass. The larger'the piece of glass,the slower the cooling that is required to avoid excessive mechanical and optical strains. The slowerthe cooling, the greater. the tendency. to devitrify.-- Hence glass formulations must be employed which will not result in devitrification in making the sizable pieces of glass that are to be finished in manufacturing the final optical elements such as lenses and prisms.

Our glasscompositions are of such a nature that they cannot be employedin making optical elements of the usual sizes and shapes. They have a strong devitrification tendency owingto the high proportion of, titanium dioxide, and to the necessity of avoiding expedients-that would lower the refractive index below the desired value. We have discovered, however, that these compositions can be employedfin making commercially useful elements provided these elements have athickness-not exceeding approximately two millimeters. These elements are sufficiently thin to permit of rapid cooling or quenching of the hot glass sotha t they can be brought to room temperature without devitrifying. A I

Transparent, stable and useful glasses of the published prior art, having recognized commercial optical interest have not exceeded a refractive index of approximatelyZll, and only rare and unusual glasses have exceeded a value of 1.8. The commonly used optical glasses of the socalled high-index types have not materially exceeded a refractive index value of 1.7. Our discoveries have involved the devising and study of unorthodox glass systems whose practical utility for our purpose was unpredictable, since it does not sufiice to provide the desired refractive index if the glass composition cannot be usefully employed in making transparent stable glass beads of suitable quality and cost.

The glass compositions which we employ may be generically defined as being those having refractive index (11 values of at least 2.1 and essentially consisting of metal oxide combinations designated in the following table, proportions being in percentage by weight:

The term BaO group is used to designate alkaline earth metal oxides of the group consisting of barium oxide (BaO), strontium oxide (SrO), calcium oxide (CaO), and magnesium oxide (MgO). Barium oxide is the preferred constituent of this group.

However, we can omit all members of this group, or instead use up to of zinc oxide (ZnO) or up to 30% of cadmium oxide (CdO) or combinations thereof; and we can use one or more oxides of the BaO group" in combination with ZnO or CdO. Zinc and cadmium oxides are employed for increasing the refractive index. These various possibilities are indicated in the above table.

In any event, the total amount of lead and cadmium oxides (when either or both is used) should be balanced in relation to the amount of bismuth oxide employed; hence the condition that the total of BizOa plus PbO plus CdO be in the range of 10 to 70%. This means that when the bismuth oxide proportion has the maximum value of 65% the total amount of lead and cadmium oxides should not exceed 5%; but they may be used in greater proportion when a smaller proportion of bismuth oxide is used.

We have found that small amounts of the so-called strong glass-forming oxides may be included as optional modifying agents, having the desirable property of improving meltability, homogeneity and vitreosity, without preventing the obtaining of refractive indices above 2.1 and other desired properties. The fact that these oxides can be omitted is a distinguishing characteristic of our primary composition that demonstrates a qualitative difference from compositions that require a relatively large proportion of strong glass-forming oxide. By strong glassforming oxides, reference is made to boric oxide (B203), silicon dioxide (SiOz), phosphorous pentoxide (P205) and germanium oxide (GeOz). The total amount of these oxides (when used) should not exceed 10%, and the amount of B203 preferably should not exceed 6%.

Our glasses are further characterized by the absence in any substantial amount of the oxides of alkali metals, which are preferably entirely absent and in no event should total more than 5% The presence as modifying agents of small amounts of other metal oxides known to be useful in glass compositions is not precluded when suitable in the particular composition in which incorporated; such as tungsten oxide (W03), Zirconium oxide (ZrOz), thorium oxide (Th02), cerium oxide (CezOs), vanadium oxide (V205), thallium oxide (T1203), lanthanum oxide (LazOa), etc. Elements such asarsenic and antimony cause rapid solarization, i. e., a darkening or change of color on exposure of the glass to sunlight, and are in general to be avoided.

In accord with general practice, our glass compositions are reported in terms of percentage by weight of oxide components presumptively present based on proportions of the oxide-forming elements known to be present in the batch or determined by analysis. It will be recognized that compounds other than oxides can be added in compounding the original glass-making charge, in amounts calculated to provide the desired amount of oxide. For example, bismuth nitrate may be used to provide the BizOa component; litharge, red lead, lead ntirate, etc., may be used to provide the PbO component; and BaCOa, HaBOa, SrCOa, MgCOa, CaCOs, CdCOa may be used to provide BaO, B203, SrO, MgO, CaO and CdO, respectively. Ordingrily, TiOz, SiOz, P205 and ZnO will be incorporated as suc In making the present glasses, the batch in powdered form (including cullet from previous runs when available) is mixed uniformly and melted in an alumina vessel. The melting temperature is in the range of 1200 to 1400' C.

Our preferred glasses may be referred to as being of the TiO2'-'Bi2OaPbO-BaO type and, consistent with the requirements previously stated, contain approximately 20 to 45% TiOz, 15 to 55% BiaOs, 5 to 45% PhD, 5 to 35% BaO (the total of these four oxides being to 99% and the total of BizOa and PbO being at least 50%), and 1 to 6% (total) of one or more strong glass-forming oxides (B203, SiOz, P205 and GeOz); the glasses consisting substantially entirely of these oxides and having refractive indices of at least 2.15.

The following are illustrate formulas, the first of which (A) has been utilized on a large commercial scale in the manufacture of glass beads for reflex-reflector products. Proportions are in percent by weight.

The following equivalent table shows the proportions on a cationic mole percent basis:

43. 8 46. 7 30. 7 l5. 3 26. 4 20. 4 20. 7 5. l 5. 3 ll. 4 l2. 5 8. 0 21. 3 2. 6 2. 8 6. 2 (l. 5 8. d

A suitable batch formulation for making Formula- A is one composed of 23.9% titanium dioxide, 23.9% bismuth oxide, 29.7% red lead, 3.4% lead metaphosphate, 15.3% barium carbonate, and 3.8% silicon dioxide, by weight.

The invention is further illustrated by the exemplary glass compositions set forth in the following tables, all of which have been used in making useful transparent glass beads having refractive indices of at least 2.1, the respective values being given in the tables. 

1. TRANSPARENT GLASS BEADS HAVING A DIAMETER NOT EXCEEDING 10 MILS, FORMED FROM GLASS CHARACTERIZED BY HAVING A REFRACTIVE INDEX OF AT LEAST 2.1 AND ESSENTIALLY CONSISTING OF A METAL OXIDE COMBINATION MEETING THE COMPOSITION REQUIREMENTS OF THE FOLLOWING TABLE WHEREIN PROPORTIONS ARE IN PERCENT BY WEIGHT: 